Azo compounds which contain a 1-sulfo-6-carboxy-2-aminonaphthalene diazo component radical and use thereof as dyes

ABSTRACT

There are disclosed azo compounds conforming to formula (1) shown and defined hereinafter, and the preparation thereof. They have fiber-reactive properties and are used for preparing strong and fast dyeings on hydroxy- and/or carboxamido-containing material, preferably fiber material, such as synthetic polyamide, wool and in particular cellulose fibers. ##STR1## where: M is hydrogen or a salt-forming metal, 
     K o  is a radical of the formula (2A) or (2B) ##STR2## where Z is a radical of the formula (3) ##STR3## where R o  is hydrogen or lower alkyl which may be substituted by certain substituents, G is halogen, methoxy, hydroxy or substituted or unsubstituted anilino, Z 1  is a radical of the formula (3a) or (3b) ##STR4## 
     
         --alk--SO.sub.2 --Y 
    
     and wherein A, B, R*, R&#34;, Y, a, k, D, E and K are as defined in the specification.

The present invention relates to the field of fiber-reactive azo dyes.

Fiber-reactive azo dyes having 2-aminonaphthalenedisulfonic acids asdiazo component are known in large numbers, for example from JapanesePatent Application Publications Sho-59-133 216, Sho-60-23 453 andSho-62-220 538 and from European Patent Application Publications Nos 0I28 034 and 0 239 847. The ever higher standards expected of thequality, the economics and the brilliance of dyeings have made itnecessary to develop new azo dyes which possess improved properties inthese respects and are simple to use

The present invention, then, provides novel azo compounds which conformto the formula (1) ##STR5## where M is hydrogen or a salt-forming metalatom, in particular an alkali metal atom, such as sodium, potassium orlithium,

K^(o) is a radical of the formula (2A) or (2B) ##STR6## where M is asdefined above,

Z is a radical of the formula (3) ##STR7## where R^(o) is hydrogen oralkyl of 1 to 4 carbon atoms, such as methyl or ethyl, or is alkyl of 1to 4 carbon atoms, such as ethyl, which is substituted by sulfo,carboxyl, sulfato, phosphato, hydroxyl, methoxy, ethoxy, phenyl,monosulfophenyl or disulfophenyl, the preferred meaning being hydrogen,

G is halogen, such as fluorine or chlorine, methoxy, hydroxyl or asubstituted or unsubstituted anilino radical which may contain afiber-reactive group, such as, for example, a phenylamino radical whichmay be substituted by a fiber-reactive group of the formula -SO₂ -Y,where Y is as defined hereinafter, and/or substituted by 1 or 2substituents selected from the group consisting of methyl, ethyl,methoxy, ethoxy, chlorine and sulfo, and

Z¹ is a radical of the formula (3a) or (3b) ##STR8##

    --alk--SO.sub.2 --Y                                        (3b)

where

A is a direct bond, alkylene of 2 to 6 carbon atoms, or phenylene whichmay be substituted by 1 or 2 substituents selected from the groupconsisting of methyl, ethyl, methoxy, ethoxy, chlorine, sulfo andcarboxyl,

B is a benzene or naphthalene radical,

R* is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and inparticular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy or inparticular methoxy, fluorine, bromine, chlorine, sulfo, carboxyl,carbalkoxy of 2 to 5 carbon atoms, such as carbomethoxy and carboethoxy,trifluoromethyl, carbamoyl or N-(C₁ -C₄ -alkyl)carbamoyl, preferablyhydrogen, methoxy or methyl if B is a benzene ring, or is hydrogen orsulfo if B is a naphthalene ring,

R" is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and inparticular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy or inparticular methoxy, chlorine, nitro or sulfo, preferably hydrogen,methoxy, ethoxy, methyl or sulfo if B is a benzene ring, or is hydrogenor sulfo if B is a naphthalene radical,

Y is vinyl or an ethyl group which contains in the β-position asubstituent which is eliminable under alkaline conditions to leave avinyl group, the Y in the subformula G being identical to or differentfrom the Y in the group bonded to B,

alk is alkylene of 2 to 6 carbon atoms, preferably 1,3-propylene,

a is zero, 1 or 2, preferably zero, and

k is 1 or 2, preferably 1,

D is a radical of the formula (4) ##STR9## where M is as defined above,

R¹ is hydrogen or alkyl of 1 to 4 carbon atoms, such as ethyl or inparticular methyl, and the -SO₃ M group is preferably bonded to thebenzene nucleus in the ortho-position relative to the free bond attachedto the azo group,

E is a radical of the formula (5a), (5b), (5c) or (5d) ##STR10## where Ris hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl, cyano,carboxyl, carbalkoxy of 2 to 5 carbon atoms, such as carbomethoxy orcarboethoxy, carbamoyl or phenyl, preferably methyl, carboxyl,carbomethoxy or carboethoxy,

Q is a benzene or naphthalene radical,

R² is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl or inparticular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy or inparticular methoxy, fluorine, bromine, chlorine, sulfo, carboxyl,carbalkoxy of 2 to 5 carbon atoms, such as carbomethoxy or carboethoxy,trifluoromethyl, carbamoyl or N-(C₁ -C₄ -alkyl)-carbamoyl, preferablyhydrogen, methoxy or methyl, if Q is a benzene ring, or is hydrogen orsulfo if Q is a naphthalene ring, `R³ is hydrogen, alkyl of 1 to 4carbon atoms, such as ethyl or in particular methyl, alkoxy of 1 to 4carbon atoms, such as ethoxy or in particular methoxy, chlorine orsulfo, preferably hydrogen, methoxy, ethoxy or methyl, if Q is a benzeneradical, or is hydrogen or sulfo if Q is a naphthalene radical,

R⁴ is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl or inparticular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy or inparticular methoxy, bromine, chlorine, trifluoromethyl, sulfo, carboxylor cyano, preferably hydrogen, methyl or sulfo,

R⁵ is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl or inparticular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy or inparticular methoxy, chlorine, amino, alkylamino of 1 to 4 carbon atoms,such as ethylamino, alkanoylamino of 2 to 5 carbon atoms, such asacetylamino or propionylamino, benzoylamino, ureido, N'-phenylureido,N'-(C₁ -C₄ -alkyl)-ureido, phenylsulfonyl or alkylsulfonyl of 1 to 4carbon atoms, such as ethylsulfonyl or methylsulfonyl, preferablyureido, acetylamino or propionylamino,

R⁶ is hydrogen or sulfo,

M is as defined above,

m is 1 or 2,

v is zero or 1, and

-K-N(R^(o))- is the bivalent radical of a water-soluble amino-containingcoupling component, such as, for example, a radical of the formula (6a),(6b) (6c), (6d), (6e), (6f), (6g), (6h) or (6i) ##STR11## where M, m, v,Q, D, R, R^(o), R¹, R², R³, R⁴, R⁵ and R⁶ are each as defined above,

V is a direct, covalent bond or a radical of the formula-NH-CO-phenylene-, -NH-CO-NH-phenylene-,-N(CH₃)-CO-phenylene-,-N(CH₃)-CO-NH-phenylene-or -NH-phenylene-,

W is a phenylene radical which may be substituted by 1 or 2 substituentsselected from the group consisting of alkyl of 1 to 4 carbon atoms, suchas ethyl or in particular methyl, alkoxy of 1 to 4 carbon atoms, such asethoxy or in particular methoxy, chlorine, carboxyl and sulfo, oralkylene of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms, suchas, for example, ethylene, or alkylene-phenylene having an alkylenemoiety of 2 to 4 carbon atoms, such as, for example, methylene-phenyleneor ethylene-phenylene,

R⁸ is hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl, alkoxy of1 to 4 carbon atoms, such as methoxy, phenyl or cyano-substituted alkylof 1 to 4 carbon atoms, and

R⁹ is hydrogen, sulfo, sulfoalkyl of 1 to 4 carbon atoms, such assulfomethyl, cyano or carbamoyl.

E is to be understood as the radical of a couplable and diazotizablecompound conforming to formula H-E-NH₂.

Alkali-eliminable substituents for ethyl Y are for example halogenatoms, such as bromine and chlorine, ester groups of organic carboxylicand sulfonic acids, such as alkanoyloxy of 2 to 5 carbon atoms, forexample acetyloxy, or sulfobenzoyloxy, benzoyloxy, phenylsulfonyloxy ortoluylsulfonyloxy, also for example the acid ester groups of phosphoricacid, of sulfuric acid and of thiosulfuric acid (phosphato, sulfato andthiosulfato groups respectively), and also dialkylamino groups havingalkyl groups each of 1 to 4 carbon atoms, such as dimethylamino anddiethylamino. Preferably, Y is vinyl or in particular β-sulfatoethyl.

The terms "sulfo", "carboxyl", "thiosulfato", "phosphato" and "sulfato"as used hereinbefore and hereinafter are meant to imply not only theacid form but also the salt form of these groups. Accordingly, sulfodenotes groups conforming to the formula --SO₃ M, carboxyl denotesgroups conforming to the formula --COOM, thiosulfato denotes groupsconforming to the formula --S--SO₃ M, phosphato denotes groupsconforming to the formula --OPO₃ M₂ and sulfato denotes groupsconforming to the formula --OSO₃ M, in each case with M of theabovementioned definition.

In the formulae (5b), (6b) and (6c), the hydroxyl group and the freebond are in each case ortho to each other within the same aromaticnucleus Preferably, the hydroxyl group is bonded to the naphthaleneradical in the α-position.

Preferably, B is a phenylene radical in which case a is preferably zeroand k is 1 and the --SO₂ --Y group is preferably bonded to the phenyleneradical meta or para to the --NH--A-- group. Furthermore, preferably R*is hydrogen, methoxy or sulfo, and also preferably R" is hydrogen,methyl or methoxy.

Preference is further given to compounds of the formula (1) in which Gis chlorine or fluorine. Preference is also given to compounds of theformula (1) in which A is a direct bond.

Fiber-reactive groupings Z conforming to the formula (3) are for examplethe4-chloro-6-[β-(4'-β'-sulfatoethylsulfonylphenyl)ethyl]amino-1,3,5-triazin-2-ylamino,4-chloro-6-(4'-β-sulfatoethylsulfonylphenyl)amino-1,3,5-triazin-2-ylamino,4-fluoro-6-(3'-β-sulfatoethylsulfonylphenyl)amino-1,3,5-triazin-2-ylamino,4-fluoro-6-(4'-β-sulfatoethylsulfonylphenyl)amino-1,3,5-triazin-2-ylamino,4-chloro-6-(3'-β-sulfatoethylsulfonylphenyl)amino-1,3,5-triazin-2-ylamino,4-chloro-6-[2'-sulfo-5'-(β-sulfatoethylsulfonyl)phenyl]amino-1,3,5-triazin-2-ylaminoand4-fluoro-6-[β-(4'-β'-sulfatoethylsulfonylphenyl)ethyl]-amino-1,3,5-triazin-2-ylaminoradicals and also other radicals evident from the Examples.

Preferred azo compounds of the formula (1) where K^(o) has the formula(2A) are in particular those in which K^(o) is a radical of the formula(7a), (7b), (7c), (7d), (7e) or (7f) ##STR12## especially of the formula(7a) or (7b), where

M is as defined above,

Z^(o) is a radical of the formula (3A) ##STR13## where G and Z¹ eachhave the above, in particular the preferred, meanings,

m₁ is zero or 1 (if zero, this group being hydrogen),

W^(o) is alkylene of 2 to 4 carbon atoms or phenylene,

R¹¹ is carboxyl, methyl or carboethoxy,

R¹² is hydrogen, methyl, methoxy, sulfo or chlorine,

R¹³ is hydrogen, methyl or methoxy, and

R¹⁴ is methyl or amino,

and particular preference is also given to compounds conforming to theformulae (1A), (1B), (1C), (1D) and (1E) ##STR14## where D, Y and M haveone of the abovementioned, particularly preferred meanings, m: is zeroor 1 and G is chlorine or fluorine.

K^(o) of the formula (2A) is for example1-[4'-chloro-6'-(4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-8-hydroxy-3,6-or -4,6-disulfonaphth-7-yl,2-[4'-chloro-6'-(4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-8-hydroxy-6-sulfonaphth-7-yl,3-[4'-chloro-6'-(4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-8-hydroxy-6-sulfonaphth-7-yl,1-[4'-fluoro-6'-(4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-8-hydroxy-3,6-or -4,6-disulfonaphth-7-yl,2-[4'-fluoro-6'-(4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-8-hydroxy-6-sulfonaphth-7-yl,3-[4'-fluoro-6'-(4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-8-hydroxy-6-sulfonaphth-7-yl,1-{4'-chloro-6'-[β-(4"-β"-sulfatoethylsulfonylphenyl)-ethylamino]-s-traizin-2'-yl}amino-8-hydroxy-3,6-or-4,6-disulfonaphth-7-yl,1-[4'-chloro-6'-(3"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-8-hydroxy-3,6-or-4,6-disulfonaphth-7-yl,1-[4'-chloro-6'-(2"-sulfo-4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-8-hydroxy-3,6-disulfonaphth-7-yl,1-{4'-chloro-6'-[β-(2"-sulfo-4"-β"-sulfatoethylsulfonylphenyl)ethyl]amino-s-triazin-2'-yl}amino-8-hydroxy-3,6-disulfonaphth-7-yl,1-{4'-fluoro-6'-[β-(3"-β"-sulfatoethylsulfonylphenyl)ethyl]amino-s-triazin-2'-yl}amino-8-hydroxy-3,6-di-sulfonaphth-7-yl,1-{4'-chloro-6'-[γ-(β'-sulfatoethylsulfonyl)propyl]amino-s-triazin-2'-yl}amino-8-hydroxy-3,6-disulfonaphth-7-yl-,1-[4'-chloro-6'-(2"-sulfo-5"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-8-hydroxy-3,6-disulfonaphth-7-yl,1-[4'-methoxy-6'-(4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-8-hydroxy-3,6-disulfonaphth-7-yl,1-[4'-chloro-6'-(4"-vinylsulfonylphenyl)amino-s-triazin-2'-yl]amino-8-hydroxy-3,6-disulfonaphth-7-yl,1-[4'-chloro-6'-(4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-4-sulfo-8-hydroxynaphth-7-yl,1-[4'-chloro-6'-(3"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-4-sulfo-8-hydroxynaphth-7-yl,1-{4'-chloro-6'-[β-(4"-β"-sulfatoethylsulfonylphenyl)ethyl]amino-s-triazin-2'-yl}-amino-3-acetylaminophenyl,1-[4'-chloro-6'-(4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-3-acetylaminophenyl,1-[4'chloro-6'-(4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-3-propionylaminophenyl,1-[4'-chloro-6'-(4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-3-ureidophenyl,1-[4'-fluoro-6'-(3"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-3-ureidophenyl,1-[4'-fluoro-6'-(4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-3-ureidophenyl,1-[4'-chloro-6'-(3"-β-sulfatoethyl-sulfonylphenyl)amino-s-triazin-2'-yl]amino-3-ureidophenyl,1-[4'-chloro-6'-(2"-sulfo-5"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-3-(N'-phenylureido)phenyl,1-{4'-fluoro-6'-[γ-(β'-sulfatoethylsulfonyl)propyl]amino-s-triazin-2'-yl}amino-3-(N'-methylureido)phenyl,1-[4'-fluoro-6'-(4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-3-acetylaminophenyl,1-[4'-fluoro-6'-(4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-3-methylphenyl,1-[4'-fluoro-6'-(2"-sulfo-4"-β-sulfatoethylsulfonylphenyl)-amino-s-triazin-2'-yl]amino-3-acetylaminophenyland 1-[4'-fluoro-6'-(4"-β-sulfatoethylsulfonylphenyl)amino-s-triazin-2'-yl]amino-3-ureidophenyl.

The present invention also provides processes for preparing the azocompounds of the formula (1) according to the present invention, whichcomprise if K^(o) is a radical of the formula (2A) coupling of thediazonium compound of an amine of the formula (8) ##STR15## where M, Eand v are each as defined above, with a compound of the formulaH--K--N(R^(o))--Z, where K, R^(o) and Z are each as defined above, orreacting a compound of the formula (9) ##STR16## where M, E, v, R^(o)and K are each as defined above, with a compound of the formula Hal-Z,where Z is as defined above and Hal is halogen, such as chlorine orfluorine, or condensing a compound of the formula (10) ##STR17## whereHal, M, E, v, R^(o), K and G are each as defined above, with a compoundof the formula (11a) or (11b) ##STR18##

    H.sub.2 N--alk--SO.sub.2 --Y                               (11b)

where A, B, R*, R", a, k, Y and alk are each as defined above, or if K°is a radical of the formula (2B) coupling a compound of the formula (12)##STR19## where M is as defined above, with the diazonium compound of anamine of the formula (13)

    H.sub.2 N--D--N(R.sup.o)--Z                                (13)

where D, R^(o) and Z are each as defined above, or reacting a compoundof the formula (14) ##STR20## where D, R^(o) and M are each as definedabove, with a compound of the formula Hal-Z, where Hal and Z are each asdefined above, or condensing a compound of the formula (15) ##STR21##where G, D, R^(o) and M are each as defined above, with a compound offormula (11a) or (11b).

The diazotization and coupling reactions of the process according to thepresent invention are carried out in a conventional manner, for instancethe diazotization in general at a temperature between -5° C. and +15° C.and at a pH below 2 by means of a strong acid and an alkali metalnitrite in a preferably aqueous medium and the coupling reaction ingeneral at a temperature between 0° and 30° C. and at a pH between 1 and4.5 in the case of an amino-containing coupling component, and at a pHbetween 3 and 7.5 in the case of a hydroxyl-containing couplingcomponent, preferably in an aqueous medium.

The starting compounds of the formula (8) where v is 1 are prepared fromthe 1-sulfo-6-carboxy-2-aminonaphthalene as diazo component and from thecompound of the general formula H-E-NH₂ as coupling component in theknown manner of diazotization and coupling reactions. The azo compoundsof the formula (12) are synthesized in the same way by coupling thediazonium salt of 1-sulfo-6-carboxy-2-aminonaphthalene with1-amino-8-naphthol-3,6- or -4,6-disulfonic acid in a strongly acidmedium in a conventional manner.

The starting compounds conforming to the formula H--E--NH₂ and to theformulae (11a) and (11b) are known and have been repeatedly described inthe literature.

Starting compounds of the formula H--E--NH₂ are for example aniline,3-methylaniline, 3-chloroaniline, 2,5-dimethylaniline,2,5-dimethoxyaniline, 3-methoxyaniline, 3-methyl-6-methoxyaniline,3-ureidoaniline, 3-acetyl-amino-6-methylaniline,2-amino-4-acetylaminobenzene-1sulfonic acid, 1-aminonaphthalene,1-aminonaphthalene-6- or -7- or -8-sulfonic acid, 3-acetylaminoaniline,2-methylaniline,2-methoxyaniline,3-benzoylaminoaniline,2,3-dimethylaniline, 3,5-dimethylaniline,2-methoxy-5-acetylaminoaniline, 2-chloro-6-methylaniline,5-chloro-2-methylaniline, 2,6-dichloro-3-methylaniline and2-methoxy-5-methylaniline.

Starting compounds of the formula H--K--N(R^(o))--H are for example1-(3'- or 4'-aminophenyl)-3-carboxy-5-pyrazolone,1-(2'-sulfo-5'-aminophenyl)-3-carboxy-5-pyrazolone,1-(2'-methoxy-5'-aminophenyl)-3-carboxy-5-pyrazolone, 1-(3'- or4'-aminophenyl)-3-methyl-5-pyrazolone,1-(6'-amino-4',8'-disulfonaphth-2'-yl)-3-carboxy-5-pyrazolone,1-amino-3,6- or -4,6-disulfo-8-naphthol, 7-amino-3-sulfo-1-naphthol,6-amino-3-sulfo-1-naphthol, 6-amino-3,5-disulfo-1-naphthol,3-methylaniline, 3-chloroaniline, 2,5-dimethylaniline,2,5-dimethoxyaniline, aniline, 3-methoxyaniline,3-methyl-6-methoxyaniline,3-ureidoaniline,3-acetylamino-6-methylaniline,2-amino-4-acetylaminobenzene-1-sulfonicacid, 1-aminonaphthalene, 1-aminonaphthalene-6- or -7- or -8-sulfonicacid, 3-acetylaminoaniline, 2-methylaniline, 2-methoxyaniline,3-benzoylaminoaniline,2,3-dimethylaniline,3,5-dimethylaniline,2-methoxy-5-acetylaminoaniline, 2-chloro-6-methylaniline,5-chloro-2-methylaniline, 2,6-dichloro-3-methylaniline,2-methoxy-5-methylaniline, 4-(phenylazo)-aniline,3-propionylaminoaniline, 3-butyrylaminoaniline,2-sulfo-5-acetylaminoaniline, 2-amino-5-naphthol-7-sulfonic acid,2-amino-8-naphthol-6-sulfonic acid, 6-methylamino-3-sulfo-1-naphthol,1-amino-3,6- or -4,6-disulfo-8-naphthol, 6-amino-3,5-disulfo-1-naphthol,6-(4'-aminophenyl)amino-3-sulfo-1-naphthol,1-amino-2,4-disulfo-8-naphthol,1-(4'-aminobenzoylamino)-3,6-disulfo-8-naphthol,1-(3'-aminobenzoylamino)-3,6-disulfo-8-naphthol,1-(4'-amino-2'-sulfophenyl)-3-carboxy-5-pyrazolone,1-(4'-amino-2'-sulfophenyl)-3-methyl-5-pyrazolone,1-(3'-sulfo-6'-methyl-5'-aminophenyl)-3-carboxy-5-pyrazolone,1-{4'-[N'-(4"-sulfo-3"-aminophenyl)carbamoyl]phenyl}-3-methyl- or-3-carboxy-5-pyrazolone, N(3,5-disulfo-4-amino)acetoacetylanilide,N-(3-sulfo-4-amino-6-methoxy)acetoacetylanilide,2-hydroxy-5-carbamoyl-4-methyl-1-(β-aminoethyl)-6-pyridone and 2-hydroxy-5-sulfomethyl-4-methyl-1-(β-aminoethyl)-6-pyridone.

Starting compounds of the formulae (11a) and (11b) are for example2-(β-sulfatoethylsulfonyl)aniline, 3-(β-sulfatoethylsulfonyl)aniline,4-(β-sulfatoethylsulfonyl)aniline,2-carboxy-5-(β-sulfatoethylsulfonyl)aniline,2-chloro-3-(β-sulfatoethylsulfonyl)aniline,2-chloro-4-(β-sulfatoethylsulfonyl)aniline, 2-ethoxy-4- or-5-(β-sulfatoethylsulfonyl)aniline,2-ethyl-4-(β-sulfatoethylsulfonyl)aniline,2-methoxy-5-(β-sulfatoethylsulfonyl)aniline,2,4-diethoxy-5-(β-sulfatoethylsulfonyl)aniline,2,4-dimethoxy-5-(β-sulfatoethylsulfonyl)aniline,2,5-dimethoxy-4-(β-sulfatoethylsulfonyl)aniline,2-methoxy-5-methyl-4-(β-sulfatoethylsulfonyl)aniline, 2- or 3- or4-(β-thiosulfatoethylsulfonyl)aniline,2-methoxy-5-(β-thiosulfatoethylsulfonyl)aniline,2-sulfo-4-(β-phosphatoethylsulfonyl)aniline,2-sulfo-4-vinylsulfonylaniline, 2-hydroxy-4- or-5-(β-sulfatoethylsulfonyl)aniline, 2-chloro-4- or-5-(β-chloroethylsulfonyl)aniline,2-hydroxy-3-sulfo-5-(β-sulfatoethylsulfonyl)aniline, 3- or4-(β-acetoxyethylsulfonyl)aniline,2-methoxy-4-[β-(N-methyltauryl)ethylsulfonyl]aniline,5-(β-sulfatoethylsulfonyl)-2-aminonaphthalene, 6- or 7- or8-(β-sulfatoethylsulfonyl)-2-aminonaphthalene,6-(β-sulfatoethylsulfonyl)-1-sulfo-2-aminonaphthalene,5-(β-sulfatoethylsulfonyl)-1-sulfo-2-aminonaphthalene,8-(β-sulfatoethylsulfonyl)-6-sulfo-2-aminonaphthalene and alsoγ-(β'-sulfatoethylsulfonyl)propylamine andγ-(β'-chloroethylsulfonyl)propylamine.

The condensation reaction between an amino starting compound of theformula (9) or (14) and a compound of the formula Hal-Z is carried outin the usual manner of reacting an amino compound with a triazinecompound which contains a reactive halogen atom, for instance in anorganic or preferably aqueous-organic medium, particularly preferably inan aqueous medium, in the presence of an acid-binding agent, such as analkali metal or alkaline-earth metal carbonate, alkali metal oralkaline-earth metal bicarbonate or hydroxide or an alkali metalacetate, the alkali and alkaline-earth metals preferably being sodium,potassium or calcium or a tertiary amine, such as, for example,pyridine, triethylamine and quinoline. If these condensation reactionsare carried out in an organic or aqueous-organic medium, the organicsolvent (component) is acetone, dioxane or dimethylformamide.

The condensation reactions between these amino compounds and the Hal-Zcompound are in general carried out at a temperature between -10° C. and+60° C., preferably between 30° and 45° C., and at a pH between 2 and 7,preferably between 2 and 4. The reaction with a compound Hal-Z where Halis fluorine is carried out particularly preferably at a pH between 3 and5 and at a temperature between 0° C. and 30° C. The reaction with Hal-Zwhere Hal is chlorine, in particular the reaction with a compound of theformula (16) ##STR22## where Z¹ is as defined above, is carried outparticularly preferably at a pH between 2.0 and 4.5 and at a temperaturebetween 30° and 45° C.

The condensation reaction between a halotriazinylamino compound of theformula (10) or (15) and an amino compound conforming to the formulae(11) is similarly carried out in the known manner of reacting suchhalotriazinylamino compounds with amines, including for instance in theabove-specified reaction media in the presence of an acid-binding agent.In general, the reaction is carried out at a temperature between 40° and100° C., preferably between 50° and 70° C., the particularly preferredconditions for the reaction with starting compounds in which Hal ischlorine being a temperature between 50° and 70° C. and a pH between 2and 4.

The 1-sulfo-6-carboxy-2-aminonaphthalene starting compound has not beendisclosed before. It can be prepared according to the present inventionby first sulfonating 2-naphthol-6-carboxylic acid in a sulfuricacid/sulfur trioxide mixture (oleum) having a sulfur trioxide content of0 to 65% by weight at a temperature between 0° C. and 40° C., preferablyat 0° to 10° C., to 1-sulfo-6-carboxy-2-naphthol, isolating thiscompound and then reacting it at a temperature between 100° and 160° C.in an autoclave in aqueous medium with ammonium hydrogen-sulfite. The1-sulfo-6-carboxy-2-naphthol is isolated from the reaction mixture in aconventional manner by carefully pouring the reaction batch onto ice.The precipitated product is filtered off with suction and suspended inice-water, and any sulfuric acid still present is neutralized withsodium carbonate by adjusting the suspension to a pH between 4 and 4.5.The compound can then be isolated by filtering off with suction anddrying.

The exchange of the hydroxyl group for an amino group is effectedsimilarly to a Bucherer reaction. The general procedure is to dissolvethe 1-sulfo-6-carboxy-2-naphthol in a 20-30% strength by weight aqueousammonium hydrogen sulfite solution and to react the reaction mixture inan autoclave under the abovementioned conditions. After this reactionhas ended, the batch is adjusted at room temperature with hydrochloricacid to pH 1. The mixture is subsequently stirred for about an hour, inthe course of which the sulfocarboxyaminonaphthalene compound accordingto the present invention precipitates as an inner salt, which can beisolated.

The compounds of the formula (1) according to the presentinvention--hereinafter referred to as compounds (1)--have fiber-reactiveproperties and very useful dye properties. They can therefore be usedfor dyeing (including printing) hydroxyl-containing and/orcarboxamidocontaining materials. In fact, the solutions obtained in thesynthesis of compounds (1) may directly be used as liquid dyes, with orwithout addition of a buffer substance and with or withoutconcentrating.

The compounds (1) can be separated and isolated from the aqueoussynthesis solutions by commonly known methods for water-solublecompounds, for instance by precipitation from the reaction medium withan electrolyte, for example sodium chloride or potassium chloride, orelse by evaporation of the reaction solution itself, for example byspray drying.

If the latter method of isolation is chosen, it is advisable in manycases to remove any sulfate quantities present in the solutions prior toevaporation, by precipitation as calcium sulfate and separation byfiltration.

The present invention accordingly also provides for the use of thecompounds (1) for the dyeing (including printing) of hydroxyl- and/orcarboxamido-containing materials and a process for their application tothese substrates. The materials to which they are applied are preferablyin the form of fiber materials, in particular in the form of textilefibers, such as yarns, packages and fabrics. It is possible forconventional techniques to be employed.

Hydroxyl-containing materials are such materials of natural or syntheticorigin, for example cellulose fiber materials, regenerated productsthereof and polyvinyl alcohols. Cellulose fiber materials are preferablycotton but other vegetable fibers as well, such as linen, hemp, jute andramie fibers; regenerated cellulose fibers are for example stapleviscose and filament viscose.

Carboxamido-containing materials are for example synthetic and naturalpolyamides and polyurethanes, in particular in the form of fibers, forexample wool and other animal hairs, silk, leather, nylon-6.6, nylon-6,nylon-11 and nylon-4.

The compounds (1), if used according to the present invention, can beemployed to and fixed on the substrates mentioned, in particular on thefiber materials mentioned, by the application techniques known forwatersoluble fiber-reactive dyes, in a process whereby the compound (1)is applied to or incorporated into the substrate in dissolved form andfixed thereon or therein with the action of heat or with the action ofan alkaline agent or with both measures. Such dyeing and fixingtechniques have been repeatedly described in the literature (see forexample European Patent Application Publication No. 0 181 585 A2). Thecompounds (1) are notable for high degrees of exhaustion and fixation.Especially in an exhaust technique they produce deep dyeings of a highdegree of fixation over a wide temperature range (40° to 80° C).

The dyeings according to the present invention, in particular those oncellulose fiber materials, have good light fastness properties not onlyin the dry state but also in the wet state, for example when moistenedwith perspiration solution, and also good wet fastness properties, suchas, for example good wash fastness properties at 60° to 95° C., even inthe presence of perborates, acid and alkaline milling, cross-dyeing andperspiration fastness properties, good acid and alkaline perspirationfastness properties, a high steam resistance, good acid, water and seawater fastness properties, and also a good fastness to dry heat settingand pleating and a good crock fastness. Similarly, they have anexcellent acid fading resistance (when dyed material which is stillmoist and contains acetic acid is stored).

The Examples which follow illustrate the invention. Parts andpercentages are by weight, unless otherwise stated. Parts by weight bearthe same relation to parts by volume as the kilogram to the liter.

The compounds described in these Examples by a formula diagram are shownin the form of the free acids; in general, they are prepared andisolated in the form of their alkali metal salts, such as lithium,sodium or potassium salts, and used for dyeing in the form of theirsalts.

Similarly, the starting compounds and components mentioned in the formof their free acids in the Examples which follow, in particular thetable examples, can be used in the synthesis as such or in the form oftheir salts, preferably alkali metal salts.

The absorption maxima (λ_(max)) in the visible region reported for thecompounds according to the present invention were determined on aqueoussolutions of their alkali metal salts. In the table examples, theirλ_(max) values are given in brackets after the hue; the wavelength unitis nm.

EXAMPLE A

a) 283.6 parts of 2-naphthol-6-carboxylic acid are added to 1,200 partsof 100% strength sulfuric acid with stirring and cooling at 5° to 7° C.The mixture is subsequently stirred at 10° C. for about 2 hours andthereafter at 20° C. for a further 2 hours until starting compound is nolonger detectable (which can be checked by HPLC analysis). The reactionmixture is then stirred onto 2,700 parts of ice. A precipitate forms,which is filtered off with suction and then suspended in ice-water. Thesuspension is adjusted with sodium carbonate to a pH of between 4 and4.5, and the product is filtered off with suction, washed with 10%strength aqueous sodium chloride solution and dried at 40° C. underreduced pressure.

b) 269.2 parts of 1-sulfo-6-carboxy-2-naphthol are stirred in 720 partsof an aqueous 25% strength ammonium hydrogen sulfite solution in anautoclave at 150° C. at 12 bar for about 8 hours. Thereafter thereaction mixture is cooled down and adjusted at room temperature to pH 1with hydrochloric acid. It is subsequently stirred for an hour, and thenthe precipitated inner salt of the compound according to the presentinvention is isolated in a yield of about 70% of theory.

The structure of the novel 1-sulfo-6-carboxy-2-aminonaphthalene isconfirmed by ¹ H- and ¹³ C-NMR spectroscopy and by elemental analysis.

1-Sulfo-6-carboxy-2-aminonaphthalene is diazotizable in a conventionalmanner.

EXAMPLE 1

To a solution of the diazonium salt of 27 parts of1-sulfo-6-carboxy-2-aminonaphthalene in aqueous hydrochloric acid isadded with stirring at 5° C. an aqueous suspension of 31.9 parts of1-amino-3,6-disulfo-8-naphthol, and the coupling reaction is carried outat a pH between 1 and 2. The suspension of the diazonium salt of thecondensation product prepared in aqueous hydrochloric acid by reacting18.8 parts of 1,3-phenylenediamine-4-sulfonic acid with 18.4 parts ofcyanuric chloride at a pH of 2.5 and a temperature of 10° C. is thenadded. The second coupling reaction is carried out at a pH of between 5and 6. Then an aqueous solution of 31 parts of4-(β-sulfatoethylsulfonyl)-1-(β-aminoethyl)benzene is added, and thecondensation reaction is completed at a pH between 6.0 and 6.5 and at atemperature of 30° C., and the resulting azo compound according to thepresent invention is precipitated by adding sodium chloride.

This gives a black electrolyte-containing powder of the alkali metalsalt of the compound of the formula ##STR23## which possesses very goodfiber-reactive dye properties and dyes for example cotton in fast navyshades by the dyeing and printing methods customary for fiber-reactivedyes.

EXAMPLES 2 TO 10

The table examples which follow describe further novel disazo compoundsconforming to a formula (A) ##STR24## where B^(o) is the radical of anamino compound conforming to the formula (11a), in terms of thecomponents indicated therein. They can be prepared in a manner accordingto the present invention, for example in the manner of EmbodimentExample 1. These novel disazo compounds likewise have very goodfiber-reactive dye properties and dye in particular cellulose fibermaterials in the fast deep shade indicated for that table example.

    __________________________________________________________________________    Disazo compound of the formula (A)                                            Example                                                                             D           G    NHB°  Hue                                       __________________________________________________________________________           ##STR25##  chlorine                                                                           4-(β-sulfatoethylsul- fonyl)phenylamino                                               navy                                      3                                                                                    ##STR26##  chlorine                                                                           4-(β-sulfatoethylsul- fonyl)phenylamino                                               "                                         4     "           fluorine                                                                           4-(β-sulfatoethylsul-                                                                 "                                                                fonyl)phenylamino                                      5                                                                                    ##STR27##  fluorine                                                                           4-(β-sulfatoethylsul- fonyl)phenylamino                                               "                                         6     "           fluorine                                                                           3-(β-sulfatoethylsul-                                                                 "                                                                fonyl)phenylamino                                      7     "           chlorine                                                                           3-(β-sulfatoethylsul-                                                                 "                                                                fonyl)phenylamino                                      8     "           fluorine                                                                           β-[4-(β'-sulfatoethyl-                                                           "                                                                sulfonyl)phenyl]ethyl-                                                        amino                                                  9     "           methoxy                                                                            4-(β-sulfatoethylsul-                                                                 "                                                                fonyl)phenylamino                                      10    "           chlorine                                                                           2-sulfo-4-(β-sulfato-                                                                 "                                                                ethylsulfonyl)phenyl-                                                         amino                                                  __________________________________________________________________________

EXAMPLE 11

58.2 parts of the binary condensation product of1,3-phenylenediamine-4-sulfonic acid, cyanuric chloride and4-(β-sulfatoethylsulfonyl)aniline are diazotized in aqueous hydrochloricacid in a conventional manner and then coupled under acid conditionswith a suspension of 30.8 parts of 1-amino-8-naphthol-3,6-disulfonicacid in 300 parts of water. The resulting red monoazo compound is thenadmixed with 27 parts of 1-sulfo-6-carboxy-2-aminonaphthalene diazotizedin aqueous hydrochloric acid, the batch is neutralized, and the couplingreaction to give the disazo dye is completed within the neutral range.The compound according to the present invention is precipitated withpotassium chloride. Drying leaves a black electrolyte-containing powderof the alkali metal salt of the compound of the formula ##STR28## which,applied by the dyeing and printing methods customary in industry forfiber-reactive dyes, produces reddish navy dyeings having good fastnessproperties on cotton for example.

EXAMPLES 12 TO 18

Further novel dyes conforming to a formula (B) ##STR29## are describedin the table examples which follow in terms of the components indicatedtherein. They can be prepared in a manner according to the presentinvention, for example in the manner of Embodiment Example 11, andlikewise have very good fiber-reactive dye properties. They dye inparticular cellulose fiber materials in the deep hue indicated for thattable example.

    __________________________________________________________________________    Disazo compound of formula (B)                                                Example                                                                             D           G    B°NH  Hue                                       __________________________________________________________________________    12                                                                                   ##STR30##  fluorine                                                                           4-(β-sulfatoethylsul- fonyl)phenylamino                                               navy                                      13    "           methoxy                                                                            4-(β-sulfatoethylsul-                                                                 "                                                                fonyl)phenylamino                                      14    "           chlorine                                                                           β-[2-sulfo-4-(β-sul-                                                             "                                                                fatoethylsulfonyl)-                                                           phenyl]ethylamino                                      15                                                                                   ##STR31##  chlorine                                                                           4-(β-sulfatoethylsul- fonyl)phenylamino                                               "                                         16    "           fluorine                                                                           4-(β-sulfatoethylsul-                                                                 "                                                                fonyl)phenylamino                                      17    "           fluorine                                                                           3-(β-sulfatoethylsul-                                                                 "                                                                fonyl)phenylamino                                      18    "           chlorine                                                                           3-(β-sulfatoethylsul-                                                                 "                                                                fonyl)phenylamino                                      __________________________________________________________________________

EXAMPLE 19

27 parts of 1-sulfo-6-carboxy-2-aminonaphthalene are diazotized in thepresence of hydrochloric acid and coupled to 15 parts of3-acetylaminoaniline. This azo compound is acylated with 19 parts offinely divided cyanuric chloride at a temperature of 40° C. and a pH of4.5, and the monocondensation product is reacted with 31 parts of4-(β-sulfatoethylsulfonyl)-1-(β-aminoethyl)benzene. The batch is thenneutralized, and the azo compound formed is salted out with sodiumchloride and isolated. This gives the alkali metal salt of the compoundof the formula ##STR32## which, applied in a conventional manner forfiber-reactive dyes, dyes for example cotton in deep fast reddish yellowshades.

EXAMPLES 20 TO 31

Further novel dyes conforming to a formula (C) ##STR33## in which--HN--B^(o) is the radical of a starting amine of the formulae (11) andK is the radical of an amino-containing coupling component conforming tothe formula H--K--NH₂, are described in the table examples which followin terms of the components indicated therein. They can be prepared in amanner according to the present invention, for example in the manner ofEmbodiment Example 19, and likewise have very good fiber-reactive dyeproperties and dye in particular cellulose fiber materials in the fastdeep shade indicated for that table example.

    ______________________________________                                        Azo compound of the formula (C)                                                             coupling component                                              Ex.  G        H--K--NH.sub.2                                                                              --HN--B°                                                                          Hue                                    ______________________________________                                        20   chlorine 3-acetylaminoaniline                                                                        4-(β-sulfatoethyl-                                                                  golden                                                             sulfonyl)- yellow                                                             phenylamino                                       21   chlorine 3-propionylamino-                                                                           4-(β-sulfatoethyl-                                                                  golden                                               aniline       sulfonyl)- yellow                                                             phenylamino                                       22   chlorine 3-ureidoaniline                                                                             4-(β-sulfatoethyl-                                                                  golden                                                             sulfonyl)- yellow                                                             phenylamino                                                                              (422)                                  23   fluorine "             4-(β-sulfatoethyl-                                                                  golden                                                             sulfonyl)- yellow                                                             phenylamino                                       24   fluorine "             3-(β-sulfatoethyl-                                                                  golden                                                             sulfonyl)- yellow                                                             phenylamino                                       25   chlorine "             3-(β-sulfatoethyl-                                                                  golden                                                             sulfonyl)- yellow                                                             phenylamino                                       26   chlorine 3-(N'-phenylureido)-                                                                        2-sulfo-5-(β-sul-                                                                   golden                                               aniline       fatoethylsulfonyl)-                                                                      yellow                                                             phenylamino                                       27   fluorine 3-(N'-methylureido)-                                                                        γ-(β'-sulfato-                                                                golden                                               aniline       ethylsulfonyl)-                                                                          yellow                                                             propylamine                                       28   fluorine 3-acetylamino-                                                                              4-(β-sulfatoethyl-                                                                  golden                                               aniline       sulfonyl)- yellow                                                             phenylamino                                       29   chlorine 3-methylaniline                                                                             4-(β-sulfatoethyl-                                                                  golden                                                             sulfonyl)- yellow                                                             phenylamino                                       30   chlorine 3-acetylamino-                                                                              2-sulfo-5-(β-sul-                                                                   golden                                               aniline       fatoethylsulfonyl)-                                                                      yellow                                                             phenylamino                                                                              (449)                                  31   fluorine 3-ureidoaniline                                                                             β-[4-(β'-sulfato-                                                              yellow                                                             ethylsulfonyl)-                                                                          (402)                                                              phenyl]ethylamino                                 ______________________________________                                    

EXAMPLE 32

18.4 parts of cyanuric chloride are reacted in a conventional mannerwith 31.9 parts of 1-amino-3,6-disulfo-8-naphthol in water to give themonocondensation product, which is then admixed with the solution of thediazonium salt of 1-sulfo-6-carboxy-2-aminonaphthalene in theappropriate equivalent amount; the coupling reaction takes place at a pHbetween 4 and 4.5. After the coupling reaction has ended, 30.9 parts of4-(β-sulfatoethylsulfonyl)-1-(β-aminoethyl)benzene are added, and thecondensation reaction is carried out at a pH between 5 and 6.5 and at20° C. The azo compound according to the present invention is isolatedfrom the synthesis solution in a conventional manner. This gives thesodium salt of the compound of the formula ##STR34## which dyes forexample cotton in bright red shades of very high brilliance.

EXAMPLE 33

31.9 parts of 1-amino-3,6-disulfo-8-naphthol are condensed with 18.5parts of cyanuric chloride in 50 parts of water and 200 parts of ice ata pH of 2.5 and a temperature of 10° C. Then this synthesis solution isadmixed with a solution at pH 4.5 with 28.2 parts of4-(β-sulfatoethylsulfonyl)aniline in 200 parts water, and the secondcondensation reaction is carried out at pH 5. Then the resultingsolution of the coupling component is admixed with a conventionallyprepared (hydrochloric acid, sodium nitrite) solution of the diazoniumsalt of 27 parts of 1-sulfo-6-carboxy-2-aminonaphthalene in about 450parts of water, a pH of 5 to 6 is set, and the coupling reaction iscarried out within this pH range at a temperature of about 20° C.

The azo compound according to the present invention is salted out withsodium chloride and isolated. Written in the form of the free acid ithas the formula ##STR35## and possesses very good fiber-reactive dyeproperties. Applied by the application processes customary in the art offiber-reactive dyes, it produces strong dyeings and prints in fastbluish red shades of high brilliance.

EXAMPLE 34

First 55.5 parts of cyanuric chloride are reacted in the conventionalmanner with 96 parts of 1-amino-3,6-disulfo-8-naphthol, and then theresulting monocondensation product is reacted with 84.3 parts of3-(β-sulfatoethylsulfonyl)aniline to give the dicondensation product.The aqueous synthesis solution of this dicondensation product is admixedwith the aqueous hydrochloric acid solution (about 680 parts) of thediazonium salt of 81 parts of 1-sulfo-6-carboxy-2-aminonaphthalene, a pHbetween 4 and 5 is set with sodium bicarbonate, and the couplingreaction is carried out within this pH range and at a temperature of 20°C. The azo compound formed is precipitated with sodium chloride andisolated. This gives the sodium salt of the compound of the formula##STR36##

The azo compound according to the present invention has very goodfiber-reactive dye properties. Applied by the application processes forfiber-reactive dyes, it produces strong bluish red dyeings and prints.Both short-time pad-batch dyeings and exhaust dyeings obtained at dyeingtemperatures between 40° and 80° C. show an excellent color buildup.

EXAMPLE 35

First 20 parts of cyanuric chloride are reacted in the conventionalmanner with 30 parts of 4-(β-sulfatoethylsulfonyl)aniline and then theresulting monocondensation product is reacted with 26 parts of3-amino-8-naphthol-6-sulfonic acid to give the dicondensation product.The aqueous solution of this condensation product is admixed with thehydrochloric acid diazonium salt solution of 27 parts of1-sulfo-6-carboxy-2-aminonaphthalene, a pH of 4 to 5 is set, and thecoupling reaction is carried out within this pH range and at atemperature of 15° to 20° C.

After the synthesis has ended, the azo compound according to the presentinvention is precipitated from the synthesis solution with sodiumchloride and isolated. This gives the sodium salt of the compound of theformula ##STR37##

The compound according to the present invention has very goodfiber-reactive dye properties and dyes for example cotton in brilliantreddish orange shades having good fastness properties.

EXAMPLE 36

31.9 parts of 1-amino-3,6-disulfo-8-naphthol are condensed with 18.5parts of cyanuric chloride at a pH of 2.5 and a temperature of 10° C.

At the same time 27.0 parts of 1-sulfo-6-carboxy-2-aminonaphthalene arediazotized in a conventional manner; this diazonium salt batch is thenadmixed with a solution of 9.3 parts of aniline in 50 parts by volume ofaqueous 0.5 N hydrochloric acid, the coupling reaction is carried out at20 to 30° C., and the resulting4-(1'-sulfo-6'-carboxynaphth-2'-yl)azoaniline is diazotized in aconventional manner by addition of 20 parts of aqueous 5 N sodiumnitrite solution.

The two reaction batches are combined, and the second coupling reactionis carried out at a pH of 3 to 4. Then 55.8 parts of4-(β-hydroxyethylsulfonyl)-1-(β-aminoethyl)benzene are added, and thecondensation reaction is carried out as described in Example 1. The azocompound is converted into the sulfato form, for example as described inExample 19, and isolated in that form by salting out to give the alkalimetal salt of the compound of the formula ##STR38## which dyes forexample cotton by conventional dyeing techniques in very fast reddishviolet shades.

EXAMPLES 37 TO 52

Further novel dyes conforming to a formula (D) ##STR39## are describedin the table examples below in terms of the formula (D) and the symbolsindicated therein. They can be prepared in a manner according to thepresent invention, for example as described in the above embodimentexamples, and likewise have very good fiber-reactive dye properties.Applied by the application and fixing methods customary forfiber-reactive dyes, they dye in particular cellulose fiber materials inthe deep fast shade indicated for that table example.

    ______________________________________                                        Azo compound of the formula (D)                                                             coupling component                                              Ex.  G        H--K(OH)--NH.sub.2                                                                         --HN--B°                                                                           Hue                                    ______________________________________                                        37   chlorine 1-amino-3,6-disul-                                                                         β-[2-sulfo-4-(β'-                                                               red                                                  fo-8-naphthol                                                                              sulfatoethylsul-                                                              fonyl)phenyl]ethyl-                                                           amino                                              38   chlorine 1-amino-3,6-disul-                                                                         γ-(β'-sulfatoethyl-                                                            red                                                  fo-8-naphthol                                                                              sulfonyl)-                                                                    propylamino                                        39   chlorine 1-amino-3,6-disul-                                                                         2-sulfo-(5-β-sul-                                                                    red                                                  fo-8-naphthol                                                                              fatoethylsulfonyl)-                                                           phenylamino                                        40   methoxy  1-amino-3,6-disul-                                                                         4-(β-sulfatoethyl-                                                                   red                                                  fo-8-naphthol                                                                              sulfonyl)-                                                                    phenylamino                                        41   chlorine 1-amino-4,6- 4-(β-sulfatoethyl-                                                                   red                                                  disulfo-8-naphthol                                                                         sulfonyl)-                                                                    phenylamino                                        42   chlorine 1-amino-4,6- 3-(β-sulfatoethyl-                                                                   red                                                  disulfo-8-naphthol                                                                         sulfonyl)-                                                                    phenylamino                                        43   chlorine 1-amino-4-sulfo-                                                                           4-(β-sulfatoethyl-                                                                   scarlet                                              8-naphthol   sulfonyl)-                                                                    phenylamino                                        44   chlorine 1-amino-4-sulfo-                                                                           4-(β-sulfatoethyl-                                                                   scarlet                                              8-naphthol   sulfonyl)-                                                                    phenylamino                                        45   chlorine 2-amino-6-sulfo-                                                                           4-(β-sulfatoathyl-                                                                   reddish                                              8-naphthol   sulfonyl)-  orange                                                            phenylamino (508)                                  46   fluorine 2-amino-6-sulfo-                                                                           4-(β-sulfatoathyl-                                                                   reddish                                              8-naphthol   sulfonyl)-  orange                                                            phenylamino (508)                                  47   chlorine 2-amino-7-sulfo-                                                                           4-(β-sulfatoathyl-                                                                   orange                                               5-naphthol   sulfonyl)-                                                                    phenylamino                                        48   fluorine 2-amino-7-sulfo-                                                                           4-(β-sulfatoathyl-                                                                   orange                                               5-naphthol   sulfonyl)-                                                                    phenylamino                                        49   chlorine 2-amino-6-sulfo-                                                                           3-(β-sulfatoethyl-                                                                   reddish                                              8-naphthol   sulfonyl)-  orange                                                            phenylamino (508)                                  50   chlorine 2-amino-6-sulfo-                                                                           β-[4-(β'-sulfato-                                                               reddish                                              8-naphthol   ethylsulfonyl)-                                                                           orange                                                            phenyl]ethylamino                                  51   chlorine 1-amino-3,6- 4-vinylsulfonyl-                                                                          red                                                  disulfo-8-naphthol                                                                         phenylamino                                        52   fluorine 1-amino-3,6- β-[4-(β'sulfato-                                                                red                                                  disulfo-8-naphthol                                                                         ethylsulfonyl)-                                                               phenyl]ethylamino                                  ______________________________________                                    

EXAMPLE 53

A solution at pH 6.5 of 43.5 parts of the aminodisazo compound of theformula ##STR40## in 300 parts of water is reacted at 0° to 5° C. and apH of 4.5 with 18.4 parts of cyanuric chloride (the starting aminodisazocompound is obtained in a conventional manner for such disazo compoundsby coupling the diazonium salt of 1-sulfo-6-carboxy-2-aminonaphthalenewith 7-sulfo-1-aminonaphthalene, diazotizing the resulting aminoazocompound and coupling the diazonium salt with7-sulfo-1-aminonaphthalene). The reaction product of this amino-disazocompound with cyanuric chloride is then reacted in its synthesissolution with 30.9 parts of 4-(β-sulfatoethylsulfonyl)-1-(β-aminoethyl)benzene at a temperature of 20° C. and a pH between 5and 6.5.

The disazo compound according to the present invention is isolated in aconventional manner as an alkali metal salt. Written in the form of thefree acid it has the formula ##STR41## shows very good fiber-reactivedye properties and dyes the materials mentioned in the description, suchas in particular cellulose fiber materials, for example cotton, by theapplication and fixing methods customary in the art in deep fast reddishbrown shades.

EXAMPLES 54 TO 58

The table examples which follow describe further novel disazo compoundsconforming to the formula (E) ##STR42## in terms of this formula and theindividual elements thereof, D* being 1-sulfo-6-carboxy-2-naphthyl. Theycan be prepared in a manner according to the present invention, forexample as described in Embodiment Example 53, and are likewise notablefor very good fiber-reactive dye properties. Applied by the knownapplication and fixing techniques they produce in particular on cottondeep fast dyeings and prints having the hue indicated for that tableexample.

    __________________________________________________________________________    Disazo compounds of the formula (E)                                           Ex.                                                                              (B*G*)               G    NHB°                                                                          Hue                                       __________________________________________________________________________    54                                                                                ##STR43##           chlorine                                                                           4-(β-sulfato- ethylsul- fonyl)phenyl-                                    amino  brown                                     55                                                                                ##STR44##           fluorine                                                                           4-(β-sulfato- ethylsul- fonyl)phenyl-                                    amino  reddish brown                             56                                                                                ##STR45##           chlorine                                                                           3-(β-sulfato- ethylsul- fonyl)phenyl-                                    amino  brownish orange                           57                                                                                ##STR46##           chlorine                                                                           4-(β-sulfato- ethylsul- fonyl)phenyl-                                    amino  brownish orange                           58                                                                                ##STR47##           chlorine                                                                           β-[4-(β-sul- fatoethylsul-                                          fonyl)phenyl]- ethylamino                                                            reddish brown                             __________________________________________________________________________

We claim:
 1. An azo compound conforming to the formula (1) ##STR48##where: M is hydrogen or a salt-forming metal atom,K^(o) is a radical ofthe formula (2A) or (2B) ##STR49## where M is as defined above, Z is aradical of the formula (3) ##STR50## where R^(o) is hydrogen or alkyl of1 to 4 carbon atoms or is alkyl of 1 to 4 carbon atoms which issubstituted by sulfo, carboxyl, sulfato, phosphato, hydroxyl, methoxy,ethoxy, phenyl, monosulfophenyl or disulfophenyl,G is halogen, methoxy,hydroxyl or a substituted or unsubstituted anilino radical in which oneof the substituents may also be a fiber-reactive group, and Z¹ is aradical of the formula (3a) or (3b) ##STR51##

    --alk--SO.sub.2 --Y                                        (3b)

where A is a direct bond, alkylene of 2 to 6 carbon atoms, or phenylenewhich may be substituted by 1 or 2 substituents selected from the groupconsisting of methyl, ethyl, methoxy, ethoxy, chlorine, sulfo andcarboxyl, B is a benzene or naphthalene radical, R* is hydrogen, alkylof 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, fluorine,bromine, chlorine, sulfo, carboxyl, carbalkoxy of 2 to 5 carbon atoms,trifluoromethyl, carbamoyl or N-(C₁ -C₄ -alkyl)carbamoyl, if B is abenzene ring, or is hydrogen or sulfo if B is a naphthalene ring, R" ishydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms,chlorine, nitro or sulfo, if B is a benzene ring, or is hydrogen orsulfo if B is a naphthalene radical, Y is vinyl or an ethyl group whichcontains in the β-position a substituent which is eliminable underalkaline conditions to leave a vinyl group, alk is alkylene of 2 to 6carbon atoms, a is zero, 1 or 2, and k is 1 or 2, D is a radical of theformula (4) ##STR52## where M is as defined above, andR¹ is hydrogen oralkyl of 1 to 4 carbon atoms, E is a radical of the formula (5a), (5b),(5c) or (5d) ##STR53## where R is hydrogen, alkyl of 1 to 4 carbonatoms, cyano, carboxyl, carbalkoxy of 2 to 5 carbon atoms, carbamoyl orphenyl,Q is a benzene or naphthalene radical, R² is hydrogen, alkyl of 1to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, fluorine, bromine,chlorine, sulfo, carboxyl, carbalkoxy of 2 to 5 carbon atoms,trifluoromethyl, carbamoyl or N-(C₁ -C₄ -alkyl)-carbamoyl, if Q is abenzene ring, or is hydrogen or sulfo if Q is a naphthalene ring, R³ ishydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms,chlorine or sulfo if Q is a benzene radical, or is hydrogen or sulfo ifQ is a naphthalene radical, R⁴ is hydrogen, alkyl of 1 to 4 carbonatoms, alkoxy of 1 to 4 carbon atoms, bromine, chlorine,trifluoromethyl, sulfo, carboxyl or cyano, R⁵ is hydrogen, alkyl of 1 to4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, amino,alkylamino of 1 to 4 carbon atoms, alkanoylamino of 2 to 5 carbon atoms,benzoylamino, ureido, N'-phenylureido, N'-(C₁ -C₄ -alkyl)-ureido,phenylsulfonyl or alkylsulfonyl of 1 to 4 carbon atoms, R⁶ is hydrogenor sulfo, M is as defined above, m is 1 or 2, v is zero or 1, and--K--N(R^(o))-- is the bivalent radical of a water-soluble couplingcomponent.
 2. An azo component as claimed in claim 1, wherein--K--N(R^(o))-- is a radical of the formula (6a), (6b) (6c), (6d), (6e),(6f), (6g), (6h) or (6i) ##STR54## where M, m, v, Q, D, R, R^(o), R¹,R², R³, R⁴, R⁵ and R⁶ are each as defined in claim 1,V is a direct,covalent bond or a radical of the formula -NH-CO-phenylene-,-NH-CO-NH-phenylene-, -N(CH₃)-CO-phenylene-, -N(CH₃)-CO-NH-phenylene- or-NH-phenylene-, W is a phenylene radical which may be substituted by 1or 2 substituents selected from the group consisting of alkyl of 1 to 4carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, carboxyl andsulfo, or alkylene of 1 to 6 carbon atoms, or alkylene-phenylene havingan alkylene moiety of 2 to 4 carbon atoms, R⁸ is hydrogen, alkyl of 1 to4 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl orcyano-substituted alkyl of 1 to 4 carbon atoms, and R⁹ is hydrogen,sulfo, sulfoalkyl of 1 to 4 carbon atoms, cyano or carbamoyl.
 3. An azocompound as claimed in claim 1, wherein R is methyl, carboxyl,carbomethoxy or carboethoxy.
 4. An azo compound as claimed in claim 1,wherein R* is hydrogen, methoxy or methyl if B is a benzene ring orhydrogen or sulfo if B is a naphthalene ring.
 5. An azo compound asclaimed in claim 1, wherein R" is hydrogen, methoxy, ethoxy or methyl ifQ is a benzene ring or hydrogen or sulfo if Q is a naphthalene radical.6. An azo compound as claimed in claim 1, wherein R² is hydrogen,methoxy or methyl if B is a benzene ring or hydrogen or sulfo if B is anaphthalene ring.
 7. An azo compound as claimed in claim 1, wherein R³is hydrogen, methoxy, ethoxy or methyl if Q is a benzene ring orhydrogen or sulfo if Q is a naphthalene radical.
 8. An azo compound asclaimed in claim 1, wherein R⁴ is hydrogen, methyl or sulfo and R⁵ isureido, acetylamino or propionylamino.
 9. An azo compound as claimed inclaim 1, wherein K^(o) is a radical of the formula (2B) ##STR55## whereM, D and Z are each as defined in claim 1 and R^(o) is hydrogen.
 10. Anazo compound as claimed in claim 1, wherein K^(o) is a radical of theformula ##STR56## where M, D and Z are each as defined in claim 1 andR^(o) is hydrogen.
 11. An azo compound as claimed in claim 1, wherein Ais a direct bond.
 12. An azo compound as claimed in claim 1, wherein ais zero.
 13. An azo compound as claimed in claim 1, wherein G ischlorine or fluorine.
 14. An azo compound as claimed in claim 1 of theformula ##STR57## where Y and M are each as defined in claim 1, G isfluorine or chlorine and m₁ is zero or
 1. 15. An azo compound as claimedin claim 1 of the formula ##STR58## where Y and M are each as defined inclaim 1, G is fluorine or chlorine and m₁ is zero or
 1. 16. An azocompound as claimed in claim 1 of the formula ##STR59## where M and Yare each as defined above and G is fluorine or chlorine.
 17. An azocompound as claimed in claim 1 of the formula ##STR60## where M and Yare each as defined in claim 1 and G is fluorine or chlorine.
 18. An azocompound as claimed in claim 1 of the formula ##STR61## where D, M and Yare each as defined in claim 1 and G is fluorine or chlorine.
 19. An azocompound as claimed in claim 1, wherein Y is vinyl or β-sulfatoethyl.20. A process for dyeing hydroxyl- or carboxamido-containing material orhydroxyl- and carboxamido-containing material, wherein a dye isintroduced onto or into the material and fixed by means of heat or withthe aid of an alkaline agent or with both heat and an alkaline agent,which comprises carrying out the dyeing with a compound conforming toformula (1) of claim
 1. 21. A process as claimed in claim 20, whereinsaid material is a fiber material.